CN114497398A - Hole transport material, preparation method thereof and photoelectric device - Google Patents
Hole transport material, preparation method thereof and photoelectric device Download PDFInfo
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- CN114497398A CN114497398A CN202011164506.8A CN202011164506A CN114497398A CN 114497398 A CN114497398 A CN 114497398A CN 202011164506 A CN202011164506 A CN 202011164506A CN 114497398 A CN114497398 A CN 114497398A
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- alkene
- semiconductor material
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/15—Hole transporting layers
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
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- C01B33/02—Silicon
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
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- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
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Abstract
The application belongs to the technical field of photoelectric devices, and particularly relates to a hole transport material, a preparation method thereof and a photoelectric device. The hole transport material comprises a two-dimensional alkene semiconductor material combined with a nucleophilic group and/or an electrophilic group, and the HOMO energy level of the two-dimensional alkene semiconductor material is-5 eV to-4.5 eV. The hole transport material has strong spin-orbit coupling and a certain band gap, shows excellent semiconductor characteristics and has high carrier mobility; and moreover, the HOMO energy level of the material is matched with the hole injection of the quantum dot light-emitting layer, so that the hole transmission efficiency is further improved, the potential barrier between the hole functional layer and the light-emitting layer is changed, the hole injection into the light-emitting layer is facilitated, and the electron and hole recombination efficiency in the light-emitting layer is improved.
Description
Technical Field
The application belongs to the technical field of photoelectric devices, and particularly relates to a hole transport material, a preparation method thereof and a photoelectric device.
Background
Quantum dot light emitting diodes (QLEDs) are a new generation of excellent display technology due to their advantages of high light emitting efficiency, high color purity, narrow light emission spectrum, tunable emission wavelength, etc. Currently, the major problems limiting the large-scale commercial application of QLEDs are their low device lifetime and poor stability. Among them, the most important problems are that hole transport efficiency in a hole functional layer in a device structure is too low, hole transport is insufficient, and electron transport efficiency in an electron functional layer is relatively high, resulting in unbalanced injection of electrons and holes in a light emitting layer, and supersaturation of electron number easily causes auger recombination. Therefore, the problems of luminous efficiency, brightness, service life and the like of the QLED device are influenced, and parameters in all aspects of the QLED are greatly influenced.
In order to increase the hole transport amount, materials such as metal oxides and organic polymers are often used to prepare the QLED hole transport layer. However, organic polymers have a short transport life; the metal oxide hole transport layer material has better stability and longer service life, but the hole transport efficiency is lower than that of the organic polymer. Therefore, at present, the problem of unbalanced injection of carriers in the QLED device still cannot be solved effectively, and a hole transport layer material with high transport efficiency, high use stability and long service life is still urgently needed.
Disclosure of Invention
The application aims to provide a hole transport material, a preparation method thereof and a photoelectric device, and aims to solve the problem of unbalanced hole and electron transport injection in the existing photoelectric devices such as QLEDs and the like to a certain extent.
In order to achieve the purpose of the application, the technical scheme adopted by the application is as follows:
in a first aspect, the present application provides a hole transport material comprising a two-dimensional olefinic semiconductor material incorporating nucleophilic and/or electrophilic groups, the HOMO level of the two-dimensional olefinic semiconductor material being in the range-5 eV to-4.5 eV.
In a second aspect, the present application provides a method for preparing a hole transport material, comprising the steps of:
obtaining a two-dimensional alkene material;
and performing addition reaction on the two-dimensional alkene material by adopting an electrophilic reagent and/or a nucleophilic reagent to obtain the added two-dimensional alkene semiconductor material.
In a third aspect, the present application provides an optoelectronic device comprising a hole transport layer comprising the above hole transport material, or comprising the hole transport material prepared by the above method.
The hole transport material provided by the first aspect of the present application includes a two-dimensional alkene semiconductor material combined with a nucleophilic group and/or an electrophilic group, which not only has strong spin-orbit coupling and a certain band gap, but also exhibits superior semiconductor characteristics and high carrier mobility; and moreover, the HOMO energy level of the material is matched with the hole injection of the quantum dot light-emitting layer, so that the hole transmission efficiency is further improved, the potential barrier between the hole functional layer and the light-emitting layer is changed, the hole injection into the light-emitting layer is facilitated, and the electron and hole recombination efficiency in the light-emitting layer is improved.
The preparation method of the hole transport material provided by the second aspect of the application is simple in process and suitable for industrial large-scale production and application, and the prepared added two-dimensional alkene semiconductor material has a deeper energy level and a larger forbidden bandwidth, and has better semiconductor characteristics. And the HOMO energy level of the added two-dimensional alkene semiconductor material is lowered to the hole injection range of the quantum dots, so that the hole transmission efficiency is improved, the hole injection into the light-emitting layer is facilitated, and the electron and hole combination efficiency in the light-emitting layer is improved.
According to the photoelectric device provided by the third aspect of the application, the hole transport layer comprises the two-dimensional alkene semiconductor material which has excellent electron transfer performance and extremely high hole transport capacity, and the nucleophilic group and/or the electrophilic group are/is combined in the mode that the HOMO energy level of the material is matched with the hole injection energy level of the quantum dot, so that the potential barrier between the hole functional layer and the light emitting layers such as the quantum dot is optimized, holes can be injected into the light emitting layers more conveniently, electrons and holes in the light emitting layers are injected more evenly, the carrier recombination efficiency is improved, and the photoelectric performance of the photoelectric device is improved.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings required for the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
Fig. 1 is a schematic flow chart of a method for preparing a hole transport material provided in an embodiment of the present application;
fig. 2 is a schematic positive structure diagram of a quantum dot light emitting diode provided in an embodiment of the present application;
fig. 3 is a schematic view of an inversion structure of a quantum dot light emitting diode provided in an embodiment of the present application;
wherein 1-substrate 2-anode 3-hole transport layer 4-luminescent layer 5-electron transport 6-cathode.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present application more clearly apparent, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.
In this application, the term "and/or" describes an association relationship of associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a is present alone, A and B are present simultaneously, and B is present alone. Wherein A and B can be singular or plural.
In the present application, "at least one" means one or more, "a plurality" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one (a), b, or c", or "at least one (a), b, and c", may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, and c may be single or plural, respectively.
It should be understood that, in various embodiments of the present application, the sequence numbers of the above-mentioned processes do not mean the execution sequence, some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its function and inherent logic, and should not constitute any limitation to the implementation process of the embodiments of the present application. The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the examples of this application and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
In a first aspect, the embodiments of the present application provide a hole transport material, where the hole transport material includes a two-dimensional alkene semiconductor material combined with a nucleophilic group and/or an electrophilic group, and a HOMO level of the two-dimensional alkene semiconductor material is-5 eV to-4.5 eV.
The hole transport material provided by the first aspect of the application comprises a two-dimensional alkene semiconductor material combined with a nucleophilic group and/or an electrophilic group, and on the one hand, the two-dimensional alkene semiconductor material combined with the nucleophilic group and/or the electrophilic group has an undulating two-dimensional reticular honeycomb structure, wherein the two-dimensional reticular honeycomb structure facilitates electrons to rapidly move along the edges of a reticular lattice, so that the material has excellent electron migration performance and extremely high hole transport capability; the non-completely planar single-layer fluctuating honeycomb atomic structure and the large element mass enable the honeycomb atomic structure to have strong spin-orbit coupling and a certain band gap, thereby showing excellent semiconductor characteristics, high carrier migration performance and a certain energy barrier. Because the energy barrier of the pure two-dimensional alkene semiconductor material is low, the pure two-dimensional alkene semiconductor material can be used as a charge transport level material only by being further increased through modification, and a nucleophilic group and/or an electrophilic group combined on the two-dimensional alkene semiconductor material can enable the two-dimensional alkene semiconductor material to introduce a larger energy gap, so that the HOMO energy level of the material is-5 eV to-4.5 eV, and the hole injection range of the quantum dot is explored. Therefore, the hole transmission efficiency is improved, the potential barrier between the hole functional layer and the luminescent layers such as quantum dots and the like is optimized, holes can be injected into the luminescent layers, and the electron and hole recombination efficiency in the luminescent layers is improved.
In some embodiments, in the two-dimensional olefinic semiconductor material having nucleophilic groups and/or electrophilic groups incorporated therein, the two-dimensional olefinic material comprises: at least one of carbene, silylene and germylene, wherein the two-dimensional olefin materials have two-dimensional honeycomb crystal structures and have the characteristics of high mobility, good conductivity, very high mechanical strength, good chemical stability and the like. The silylene and the germylene have certain semiconductor properties, and the carbene also has the semiconductor properties after being combined with the nucleophilic group and the electrophilic group. By adding and combining nucleophilic groups and/or electrophilic groups on silylene and germanium alkene, especially carbene, the two-dimensional reticular honeycomb structure of the material is converted into a monolayer fluctuating honeycomb atomic structure which is not completely planar, and the element mass is larger, so that the material has strong spin-orbit coupling and a larger energy gap. The HOMO energy level of the material is lowered to the hole injection range of the luminescent material, which is not only beneficial to hole transmission and migration, but also more beneficial to hole injection into the luminescent layer to be combined with electrons.
In some embodiments, the sheet diameter of the two-dimensional alkene semiconductor material is 1-10 nm. On one hand, the two-dimensional alkene semiconductor material with small and uniform sheet diameter has larger effective specific surface area, and is beneficial to the addition modification of electrophilic groups and nucleophilic groups to form the two-dimensional alkene semiconductor material combined with the nucleophilic groups and/or the electrophilic groups. On the other hand, the small-diameter material is more beneficial to preparing a hole transport film with a compact film layer, uniform thickness and smooth surface. The method is favorable for reducing interface impedance and improving the bonding tightness between the functional layer and an adjacent functional layer, so that the functional layer has better application performance in photoelectric devices. In some embodiments, the sheet diameter of the two-dimensional olefinic semiconductor material may be 1nm, 2nm, 3nm, 5nm, 4nm, 6nm, 7nm, 8nm, 9nm, or 10 nm.
In some embodiments, the electrophilic group comprises: -SO4At least one of, -F, -Cl, -Br, -I, -Cl, -OBr and-COOH. In some embodiments, the nucleophilic group comprises: -NH2At least one of-OH and-SH. In the above embodiments, the electrophilic group or the nucleophilic group is introduced into the two-dimensional alkene semiconductor material by addition, which can effectively increase the energy gap of the two-dimensional alkene semiconductor material such as carbene, silylene, germylene, etc., so that the HOMO energy level of the material is lower than the hole injection range of the quantum dotAnd (5) enclosing.
In some embodiments, from 1% to 10% of the alkene conjugated bonds in the two-dimensional alkene semiconductor material are added by electrophilic groups or nucleophilic groups to form the two-dimensional alkene semiconductor material incorporating nucleophilic groups and/or electrophilic groups. According to the embodiment of the application, the electrophilic groups and the nucleophilic groups open conjugated olefin bonds in the two-dimensional olefin semiconductor material through addition, and the electrophilic groups and the nucleophilic groups are introduced into the two-dimensional olefin semiconductor material, so that the two-dimensional olefin semiconductor material combined with the nucleophilic groups and/or the electrophilic groups has a deeper energy level and a larger forbidden bandwidth, the HOMO energy level can be expanded to-4.5-5.0 eV, and the two-dimensional olefin semiconductor material has the property of high charge transfer performance and can be used as an excellent hole transport material. If the addition ratio is too low, the deep energy level modification site of the material is lower, so that the material does not have the hole transport performance; if the addition ratio is higher than 10%, the HOMO level of the modified material tends to be too deep, which makes hole injection difficult and lowers the hole transport level. In some embodiments, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, or 10% of the alkene conjugated bonds in the two-dimensional alkene semiconductor material are added by electrophilic groups or nucleophilic groups to form the two-dimensional alkene semiconductor material incorporating nucleophilic groups and/or electrophilic groups.
The hole transport material provided in the above-described embodiments of the present application can be prepared by the following example methods.
As shown in fig. 1, a second aspect of the embodiments of the present application provides a method for preparing a hole transport material, including the steps of:
s10, obtaining a two-dimensional alkene material;
s20, performing addition reaction on the two-dimensional alkene material by adopting an electrophilic reagent and/or a nucleophilic reagent to obtain the added two-dimensional alkene semiconductor material.
In the preparation method of the hole transport material provided in the second aspect of the present application, an electrophilic reagent and/or a nucleophilic reagent is/are used to perform an addition reaction on a two-dimensional alkene material, so that an electrophilic group and a nucleophilic group are combined on the two-dimensional alkene material, and the two-dimensional alkene semiconductor material after the addition is obtained. The preparation method is simple in process and suitable for industrial large-scale production and application, and the prepared added two-dimensional alkene material is combined with electrophilic groups and nucleophilic groups, so that the two-dimensional alkene semiconductor material has deeper energy level and larger forbidden bandwidth, and has better semiconductor characteristics. And the HOMO energy level of the added two-dimensional alkene semiconductor material is lowered to the hole injection range of the quantum dots, so that the hole transmission efficiency is improved, the hole injection into the light-emitting layer is facilitated, and the electron and hole combination efficiency in the light-emitting layer is improved.
Specifically, in step S10, the obtained two-dimensional graphene material includes: at least one of carbene, silylene and germylene.
In some embodiments, the sheet diameter of the two-dimensional alkene semiconductor material is 1-10 nm.
The beneficial effects of the above embodiments of the present application are discussed in the foregoing, and are not described herein again.
Specifically, in step S20, the step of performing the addition reaction includes: and mixing the two-dimensional alkene material with gaseous electrophilic reagents and/or nucleophilic reagents with the volume concentration of 0.5-5% under the inert atmosphere at the temperature of 100-200 ℃, and reacting for 10-60 min to obtain the two-dimensional alkene semiconductor material after electrophilic addition and/or nucleophilic addition. The inert gas atmosphere comprises at least one of nitrogen, argon, helium and other gases, and the two-dimensional alkene material is prevented from being decomposed by active gases such as oxygen in the air of a high-temperature environment. The temperature environment of 100-200 ℃ can effectively ensure that the conjugated olefin bond of the two-dimensional olefin material is opened, so that the electrophilic group and the nucleophilic group are favorable for attacking and adding the conjugated bond to form the two-dimensional olefin semiconductor material combined with the nucleophilic group and/or the electrophilic group. The gaseous environment of the electrophile and/or nucleophile with the volume concentration of 0.5% -5% is not only beneficial to the attack and addition of the electrophile and the nucleophile to the two-dimensional alkene material, but also the concentration effectively controls the addition ratio of the electrophile and the nucleophile to the two-dimensional alkene material, and is beneficial to obtaining the two-dimensional alkene semiconductor material combined with the nucleophilic group and/or the electrophilic group with the conjugated alkene addition rate of 1% -10%, namely 1% -10% of alkene conjugated bonds in the two-dimensional alkene semiconductor material are added by the electrophilic group or the nucleophilic group. The poor energy level modification effect on the two-dimensional alkene semiconductor material caused by the excessively low addition ratio is avoided; meanwhile, the problems of difficult hole injection, reduced hole transfer level and the like caused by too deep HOMO energy level of the modified material due to too high addition ratio are avoided.
In some embodiments, the electrophile is selected from the group consisting of: at least one of halogen, inorganic acid and organic acid. In some embodiments, the nucleophile is selected from: at least one of amine, alcohol and mercaptan. The electrophile and the nucleophile can attack a conjugated olefin bond of the two-dimensional olefin material, open the olefin conjugated bond, graft an electrophilic group or a nucleophilic group on the two-dimensional olefin material, widen the energy level and the forbidden bandwidth of the material, enable the HOMO energy level of the material to be lower than the hole injection range of the quantum dot, and have better hole transmission and injection performance.
In some embodiments, the halogen is selected from: cl2、Br2、F2、I2At least one of (1).
In some embodiments, the inorganic acid is selected from: h2SO4At least one of HF, HCl, HBr, HI, HOCl and HOBr.
In some embodiments, the organic acid is selected from: f3C-COOH、Cl3At least one of C-COOH.
In some embodiments, the amine is selected from: at least one of ammonia gas and aliphatic amine compounds;
in some embodiments, the alcohol is selected from: at least one of aliphatic alcohol and aromatic alcohol;
in some embodiments, the thiol is selected from: at least one of aliphatic mercaptan and aromatic mercaptan.
In a third aspect of the embodiments of the present application, there is provided an optoelectronic device, which includes a hole transport layer containing the above hole transport material, or a hole transport material prepared by the above method.
According to the photoelectric device provided by the third aspect of the application, the hole transport layer comprises the two-dimensional alkene semiconductor material combined with the nucleophilic group and/or the electrophilic group, the modified material not only has excellent electron transfer performance and extremely high hole transport capacity, but also the HOMO energy level of the material is matched with the hole injection energy level of the quantum dot, so that the potential barrier between the hole functional layer and the luminescent layers such as the quantum dot is optimized, the hole injection into the luminescent layer is facilitated, the electron and hole injection in the luminescent layer are more balanced, the carrier recombination efficiency is improved, and the photoelectric performance of the photoelectric device is improved.
In some embodiments, the thickness of the hole transport layer is 30-50 nm, and within the range, the film layer uniformity of the hole transport layer is good, and the hole transport performance of the whole device is optimal. If the thickness of the hole transport layer is too high, the hole transport path is increased, and the hole transport performance of the device is reduced, so that the operating voltage is increased. In some embodiments, the hole transport layer has a thickness of 30nm, 35nm, 40nm, 45nm, and 50 nm.
In some embodiments, the hole transport layer is comprised of a two-dimensional olefinic semiconductor material that incorporates nucleophilic and/or electrophilic groups.
In the embodiment of the present application, the device is not limited by the device structure, and may be a device of a positive type structure or a device of an inverted type structure.
In one embodiment, a light emitting device of a positive type structure includes a stacked structure of an anode and a cathode which are oppositely disposed, a light emitting layer disposed between the anode and the cathode, and the anode is disposed on a substrate. Further, a hole functional layer such as a hole injection layer, a hole transport layer, an electron blocking layer and the like can be arranged between the anode and the light-emitting layer; an electron-transporting layer, an electron-injecting layer, a hole-blocking layer, and other electron-functional layers may be provided between the cathode and the light-emitting layer. In some embodiments of a specific positive-type structure device, the light-emitting device includes a substrate 1, an anode 2 disposed on a surface of the substrate 1, a hole transport layer 3 disposed on a surface of the anode 2, a light-emitting layer 4 disposed on a surface of the hole transport layer 3, an electron transport layer 5 disposed on a surface of the light-emitting layer 4, and a cathode 6 disposed on a surface of the electron transport layer 5, as shown in fig. 2.
In one embodiment, an inversion structure light emitting device includes a stacked structure of an anode and a cathode disposed opposite to each other, a light emitting layer disposed between the anode and the cathode, and the cathode disposed on a substrate. Further, a hole functional layer such as a hole injection layer, a hole transport layer, an electron blocking layer and the like can be arranged between the anode and the light-emitting layer; an electron-transporting layer, an electron-injecting layer, a hole-blocking layer, and other electron-functional layers may be provided between the cathode and the light-emitting layer. In some embodiments of the device with the inverted structure, the light emitting device comprises a substrate 1, a cathode 6 disposed on the surface of the substrate 1, an electron transport layer 5 disposed on the surface of the cathode 6, a light emitting layer 4 disposed on the surface of the electron transport layer 5, a hole transport layer 3 disposed on the surface of the light emitting layer 4, and an anode 2 disposed on the surface of the hole transport layer 3, as shown in fig. 3.
In some embodiments, the substrate is not limited to be used, and a rigid substrate or a flexible substrate may be used. In some embodiments, the rigid substrate includes, but is not limited to, one or more of glass, metal foil. In some embodiments, the flexible substrate includes, but is not limited to, one or more of polyethylene terephthalate (PET), polyethylene terephthalate (PEN), Polyetheretherketone (PEEK), Polystyrene (PS), Polyethersulfone (PES), Polycarbonate (PC), Polyarylate (PAT), Polyarylate (PAR), Polyimide (PI), polyvinyl chloride (PV), Polyethylene (PE), polyvinylpyrrolidone (PVP), textile fibers.
In some embodiments, the anode material is selected without limitation and may be selected from doped metal oxides including, but not limited to, one or more of indium-doped tin oxide (ITO), fluorine-doped tin oxide (FTO), antimony-doped tin oxide (ATO), aluminum-doped zinc oxide (AZO), gallium-doped zinc oxide (GZO), indium-doped zinc oxide (IZO), magnesium-doped zinc oxide (MZO), and aluminum-doped magnesium oxide (AMO). Or a composite electrode with metal sandwiched between doped or undoped transparent metal oxides, including but not limited to AZO/Ag/AZO, AZO/Al/AZO, ITO/Ag/ITO, ITO/Al/ITO, ZnO/Ag/ZnO, ZnO/Al/ZnO, TiO2/Ag/TiO2、TiO2/Al/TiO2、ZnS/Ag/ZnS、ZnS/Al/ZnS、TiO2/Ag/TiO2、TiO2/Al/TiO2One or more of (a).
In some embodiments, the hole injection layer includes, but is not limited to, organic hole injection materials, doped or undoped transition metal oxides, and the likeOne or more of the hetero metal chalcogenide compounds. In some embodiments, the organic hole injection material includes, but is not limited to, one or more of poly (3, 4-ethylenedioxythiophene) -polystyrenesulfonic acid (PEDOT: PSS), copper phthalocyanine (CuPc), 2,3,5, 6-tetrafluoro-7, 7',8,8' -tetracyanoquinodimethane (F4-TCNQ), 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-Hexaazatriphenylene (HATCN). In some embodiments, transition metal oxides include, but are not limited to, MoO3、VO2、WO3、CrO3And CuO. In some embodiments, the metal chalcogenide compounds include, but are not limited to, MoS2、MoSe2、WS2、WSe2And CuS.
In some embodiments, the hole transport layer comprises a two-dimensional olefinic semiconductor material incorporating nucleophilic groups and/or electrophilic groups as described above.
In some embodiments, the light emitting layer includes quantum dot materials therein, including, but not limited to: at least one of the semiconductor compounds of II-IV group, II-VI group, II-V group, III-VI group, IV-VI group, I-III-VI group, II-IV-VI group and II-IV-V group of the periodic table of the elements, or at least two of the semiconductor compounds. In some embodiments, the quantum dot functional layer material is selected from: at least one semiconductor nanocrystal compound of CdSe, CdS, CdTe, ZnO, ZnSe, ZnS, ZnTe, HgS, HgSe, HgTe and CdZnSe, or at least two semiconductor nanocrystal compounds with mixed type, gradient mixed type, core-shell structure type or combined type structures. In other embodiments, the quantum dot functional layer material is selected from the group consisting of: at least one semiconductor nanocrystal compound of InAs, InP, InN, GaN, InSb, InAsP, InGaAs, GaAs, GaP, GaSb, AlP, AlN, AlAs, AlSb, CdSeTe and ZnCdSe, or a semiconductor nanocrystal compound with a mixed type, a gradient mixed type, a core-shell structure type or a combined type of at least two components. In other embodiments, the quantum dot functional layer material is selected from: at least one of a perovskite nanoparticle material (in particular a luminescent perovskite nanoparticle material), a metal nanoparticle material, a metal oxide nanoparticle material. The quantum dot materials have the characteristics of quantum dots and have good photoelectric properties.
In some embodiments, the particle size range of the quantum dot material is 2-10 nm, the particle size is too small, the film forming property of the quantum dot material is poor, the energy resonance transfer effect among quantum dot particles is significant, the application of the material is not facilitated, the particle size is too large, the quantum effect of the quantum dot material is weakened, and the photoelectric property of the material is reduced.
In some embodiments, the material of the electron transport layer includes, but is not limited to, ZnO, TiO2、SnO、Ta2O3、AlZnO、ZnSnO、InSnO、Alq3、Ca、Ba、CsF、LiF、CsCO3And the like.
In some embodiments, the cathode material may be one or more of various conductive carbon materials, conductive metal oxide materials, metal materials. In some embodiments, the conductive carbon material includes, but is not limited to, doped or undoped carbon nanotubes, doped or undoped graphene oxide, C60, graphite, carbon fibers, porous carbon, or mixtures thereof. In some embodiments, the conductive metal oxide material includes, but is not limited to, ITO, FTO, ATO, AZO, or mixtures thereof. In some embodiments, the metallic material includes, but is not limited to, Al, Ag, Cu, Mo, Au, or alloys thereof; wherein the metal material is in the form of a compact film, a nanowire, a nanosphere, a nanorod, a nanocone, a hollow nanosphere, or a mixture thereof; preferably, the cathode is Ag or Al.
In some embodiments, the fabrication of a light emitting device of embodiments of the present application includes the steps of:
s30, obtaining a substrate deposited with an anode;
s40, growing a hole transport layer on the surface of the anode;
s50, depositing a quantum dot light-emitting layer on the hole transport layer;
and S60, finally, depositing an electron transmission layer on the quantum dot light-emitting layer, and evaporating a cathode on the electron transmission layer to obtain the light-emitting device. The deposition method includes, but is not limited to, dispensing, spin coating, dipping, coating, printing, and evaporation.
Specifically, in step S30, in order to obtain a high-quality zinc oxide nanomaterial film, the ITO substrate needs to undergo a pretreatment process. The basic specific processing steps include: and cleaning the ITO conductive glass with a cleaning agent to primarily remove stains on the surface, then sequentially and respectively ultrasonically cleaning the ITO conductive glass in deionized water, acetone, absolute ethyl alcohol and deionized water for 20min to remove impurities on the surface, and finally drying the ITO conductive glass with high-purity nitrogen to obtain the ITO anode.
Specifically, in step S40, the step of growing the hole transport layer includes: depositing a prepared solution of a hole transport material (the two-dimensional alkene semiconductor material combined with the nucleophilic group and/or the electrophilic group) on an ITO substrate to form a film in the modes of drop coating, spin coating, soaking, coating, printing, evaporation and the like; the film thickness is controlled by adjusting the concentration of the solution, the spin-coating speed and the spin-coating time, and then a thermal annealing process is performed at an appropriate temperature. In some embodiments, the concentration of the hole transport material may be 10-30 mg/mL, and the thickness of the hole transport layer is 30-50 nm.
Specifically, in step S50, the step of depositing the quantum dot light-emitting layer on the hole transport layer includes: and (3) placing the substrate on which the hole transport layer is coated on a spin coater, spin-coating the prepared luminescent substance solution with a certain concentration to form a film, controlling the thickness of the luminescent layer to be about 20-60 nm by adjusting the concentration of the solution, the spin-coating speed and the spin-coating time, and drying at a proper temperature.
Specifically, in step S60, the step of depositing the electron transport layer on the quantum dot light emitting layer includes: the method comprises the steps of carrying out spin coating on a prepared electronic transmission composite material solution with a certain concentration to form a film through processes of drop coating, spin coating, soaking, coating, printing, evaporation and the like, controlling the thickness of an electronic transmission layer to be about 20-60 nm by adjusting the concentration of the solution, the spin coating speed (preferably, the rotating speed is 2000-6000 rpm) and the spin coating time, then annealing the film at the temperature of 150-200 ℃ to form the film, and fully removing a solvent.
Specifically, in step S60, the step of cathode preparation includes: and (3) placing the substrate on which the functional layers are deposited in an evaporation bin, and thermally evaporating a layer of 60-100nm metal silver or aluminum as a cathode through a mask plate.
In a further embodiment, the obtained QLED device is subjected to a packaging process, and the packaging process may be performed by a common machine or by a manual method. Preferably, the oxygen content and the water content are both lower than 0.1ppm in the packaging treatment environment to ensure the stability of the device.
In order to make the above implementation details and operations of the present application clearly understood by those skilled in the art, and to make the progress of the hole transport material, the method for manufacturing the same, and the light emitting device of the embodiments of the present application obviously manifest, the above technical solutions are illustrated by a plurality of examples below.
Example 1
A hole transport material prepared by the steps comprising: placing the silylene nano material with the sheet diameter of 2-5 nm in a watch glass, placing the watch glass in a muffle furnace, heating to 150 ℃ in an argon atmosphere, introducing argon containing 1% of HF gas for 30min, preserving the temperature for 30min, and cooling to room temperature to obtain the fluorinated silylene nano material; 1% of the olefin conjugated bonds in the silylene nanomaterial are added by HF.
A QLED device is prepared by the following steps:
firstly, in an argon atmosphere, dispersing fluorinated silylene nano material with the sheet diameter of 2-5 nm in an ethanol solvent, wherein the concentration of the fluorinated silylene nano material in the solvent is 20mg/mL, and stirring for 30min at 25 ℃ until the fluorinated silylene nano material is completely dispersed for preparing a QLED device.
And spin-coating or depositing the hole injection layer, the hole transport layer, the quantum dot light emitting layer and the electron transport layer on the ITO substrate in sequence, and finally evaporating silver Ag on the electron transport layer to obtain the QLED device after packaging. The quantum dots are CdSeS/ZnS green quantum dots, the electron transport layer is made of zinc oxide ZnO with the sheet diameter of 2-5 nm, the hole transport layer is made of a fluorinated silylene nano material solution in the step I, and the hole injection layer is made of PEDOT: PSS material, the cathode material is silver Ag, and the anode substrate is ITO substrate.
Example 2
A hole transport material prepared by the steps comprising: placing a germanium alkene nano material with the sheet diameter of 2-5 nm in a watch glass, placing the watch glass in a muffle furnace, heating to 100 ℃ in an argon atmosphere, introducing argon containing 3% HF gas for 30min, preserving heat for 30min, and cooling to room temperature to obtain a germanium alkene fluoride nano material; 5% of the olefin conjugated bonds in the germanium alkene nanomaterial are added by HF.
A QLED device, which is different from embodiment 1 in that: the hole transport layer adopts a germanium alkene fluoride nano material.
Example 3
A hole transport material prepared by the steps comprising: placing a silylene nano material with the sheet diameter of 2-5 nm in a watch glass, placing the watch glass in a muffle furnace, heating to 200 ℃ in an argon atmosphere, introducing argon containing 5% HBr gas for 30min, preserving heat for 30min, and cooling to room temperature to obtain a silylene bromide nano material; 10% of the olefin conjugated bonds in the brominated silylene nanomaterial are added by HF.
A QLED device, which is different from embodiment 1 in that: the hole transport layer adopts a brominated silylene nano material.
Example 4
A hole transport material prepared by the steps comprising: placing a graphene nano material with the sheet diameter of 2-5 nm in a watch glass, placing the watch glass in a muffle furnace, heating to 150 ℃ in an argon atmosphere, introducing argon containing 4% HBr gas for 30min, preserving heat for 30min, and cooling to room temperature to obtain a brominated graphene nano material; 8% of the olefin conjugated bonds in the brominated graphene nanomaterial are added by HF.
A QLED device, which is different from embodiment 1 in that: the hole transport layer adopts a brominated silylene nano material.
Example 5
A hole transport material prepared by the steps comprising: placing a silylene nano material with the sheet diameter of 2-5 nm in a watch glass, placing the watch glass in a muffle furnace, heating to 150 ℃ in an argon atmosphere, introducing argon containing 1% of atomized acetic acid gas for 30min, preserving the temperature for 30min, and cooling to room temperature to prepare a silylene bromide nano material; 1% of the olefin conjugated bonds in the brominated silylene nanomaterial are added by acetic acid.
A QLED device, which is different from embodiment 1 in that: the hole transport layer adopts a brominated silylene nano material.
Example 6
A hole transport material prepared by the steps comprising: placing the silylene nano material with the sheet diameter of 2-5 nm in a watch glass, placing the watch glass in a muffle furnace, heating the watch glass to 150 ℃ in an argon atmosphere, and then introducing 2% Br2Argon gas is used for 30min, the temperature is kept for 30min, and then the temperature is reduced to room temperature, so that the silicon bromide nano material is prepared; 4% of the olefin conjugated bonds in the brominated silylene nanomaterial are added by Br.
A QLED device, which is different from embodiment 1 in that: the hole transport layer is made of a brominated silylene nano material.
Comparative example 1
A hole transport material takes a silylene nano material with the sheet diameter of 2-5 nm as a comparative example 1.
A QLED device, which is different from embodiment 1 in that: the hole transport layer is made of a silicon alkene nano material with the sheet diameter of 2-5 nm.
Comparative example 2
A hole transport material uses a germanium alkene nano material with the sheet diameter of 2-5 nm as a comparative example 2.
A QLED device, which is different from embodiment 1 in that: the hole transport layer is made of a germanium alkene nano material with the sheet diameter of 2-5 nm.
Comparative example 3
A hole transport material takes a graphene nano material with the sheet diameter of 2-5 nm as a comparative example 1.
A QLED device, which is different from embodiment 1 in that: the hole transport layer is made of graphene nano materials with the sheet diameter of 2-5 nm.
Comparative example 4
A hole transport material prepared by the steps comprising: placing a silylene nano material with the sheet diameter of 2-5 nm in a watch glass, placing the watch glass in a muffle furnace, heating to 150 ℃ in an argon atmosphere, then introducing argon containing 10% HBr gas for 30min, preserving the heat for 30min, and cooling to room temperature to obtain a silylene bromide nano material; 15% of the olefin conjugated bonds in the brominated silylene nanomaterial are added by HF.
A QLED device, which is different from embodiment 1 in that: the hole transport layer adopts a brominated silylene nano material.
Comparative example 5
A QLED device, which is different from embodiment 1 in that: the hole transport layer employs TFB.
Further, in order to verify the advancement of the hole transport material of the examples of the present application, the following performance tests were performed.
1. Hole mobility test: the current density (J) -voltage (V) of the QLED devices provided in examples 1 to 6 and comparative examples 1 to 5 were used for testing, a graph of the relationship of the curves was drawn, a Space Charge Limited Current (SCLC) region in the relationship was fitted, and then the hole mobility was calculated according to the well-known Child's law formula: j ═ 9/8 epsilonrε0μeV2/d3Wherein J represents current density in mAcm-2；εrDenotes the relative dielectric constant,. epsilon0Represents the vacuum dielectric constant; mu.seDenotes hole mobility in cm2V- 1s-1(ii) a V represents the drive voltage, in units of V; d represents the film thickness in m, and the test results are shown in table 1 below:
2. external Quantum Efficiency (EQE) test: the external quantum efficiency of the QLED devices provided in examples 1 to 6 and comparative examples 1 to 5 was measured using an EQE optical test instrument, and the test results are shown in table 1 below:
TABLE 1
As can be seen from the test results in table 1 above, the hole mobility and external quantum efficiency of the QLED devices prepared in examples 1 to 6 of the present invention are significantly higher than those of comparative examples 1 to 3 in which no addition is performed, and comparative example 4 in which the addition ratio is higher than 10% and 15%, and comparative example 5 in which a conventional hole transport material is used. It is demonstrated that the two-dimensional alkene semiconductor material combined with nucleophilic group and/or electrophilic group adopted in embodiments 1 to 6 of the present application as the hole transport layer can provide excellent hole transport effect for the QLED; meanwhile, the HOMO energy level depth of the device can be adjusted by adjusting the addition degree, so that the device is adaptive to different device types, the injection balance of electrons and holes in the device is better optimized, the carrier recombination efficiency is improved, and the QLED luminous efficiency is further improved.
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (11)
1. A hole transport material comprising a two dimensional olefinic semiconductor material incorporating nucleophilic and/or electrophilic groups, the HOMO level of the two dimensional olefinic semiconductor material being in the range-5 eV to-4.5 eV.
2. The hole transport material of claim 1, wherein the two-dimensional olefinic semiconductor material having nucleophilic and/or electrophilic groups incorporated therein comprises: at least one of carbene, silylene and germylene;
and/or the sheet diameter of the two-dimensional alkene semiconductor material is 1-10 nm.
3. The hole transport material of claim 2, wherein the electrophilic groups comprise: -SO4At least one of-F, -Cl, -Br, -I, -Cl, -OBr and-COOH;
and/or, the nucleophilic group comprises: -NH2At least one of-OH and-SH.
4. The hole transport material of claim 3, wherein 1% to 10% of the olefin conjugated bonds in the two-dimensional olefinic semiconductor material are added by electrophilic groups or nucleophilic groups.
5. A method for preparing a hole transport material, comprising the steps of:
obtaining a two-dimensional alkene material;
and performing addition reaction on the two-dimensional alkene material by adopting an electrophilic reagent and/or a nucleophilic reagent to obtain the added two-dimensional alkene semiconductor material.
6. The method for producing a hole transport material according to claim 5, wherein the step of addition reaction comprises: and mixing the two-dimensional alkene material with the gaseous electrophilic reagent and/or the gaseous nucleophilic reagent with the volume concentration of 0.5-5% under the inert atmosphere with the temperature of 100-200 ℃, and reacting for 10-60 min to obtain the two-dimensional alkene semiconductor material after electrophilic addition and/or nucleophilic addition.
7. The method for producing a hole transport material according to claim 6, wherein the electrophile is selected from the group consisting of: at least one of halogen, inorganic acid and organic acid;
and/or, the nucleophile is selected from: at least one of amine, alcohol, thiol;
and/or, the two-dimensional olefin material comprises: at least one of carbene, silylene and germylene;
and/or the sheet diameter of the two-dimensional alkene semiconductor material is 1-10 nm.
8. The method for producing a hole transport material according to claim 7, wherein the halogen is selected from the group consisting of: cl2、Br2、F2、I2At least one of;
and/or, the inorganic acid is selected from: h2SO4At least one of HF, HCl, HBr, HI, HOCl, and HOBr;
and/or, the organic acid is selected from: f3C-COOH、Cl3At least one of C-COOH;
and/or, the amine is selected from: at least one of ammonia gas and aliphatic amine compounds;
and/or, the alcohol is selected from: at least one of aliphatic alcohol and aromatic alcohol;
and/or, the thiol is selected from: at least one of aliphatic mercaptan and aromatic mercaptan.
9. An optoelectronic device comprising a hole transport layer comprising a hole transport material according to any of claims 1 to 4 or a hole transport material prepared by a process according to any of claims 5 to 8.
10. The optoelectronic device according to claim 9, wherein the hole transport layer has a thickness of 30 to 50 nm.
11. The optoelectronic device according to claim 9 or 10, wherein the hole transport layer is comprised of a two-dimensional olefinic semiconductor material incorporating nucleophilic and/or electrophilic groups.
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